Red halogen vat-dye and process of making same.



"outrun sTAtrEs PATENT OFFICE.

(,rADIEN'I ENQI, ()l HASEL, SWITZERLAND, ASSIGNOR TO THE FIRM OF SOCIETY OF UI'IELIIIAL INDUSTRY IN BASIIE, 0F BASEL, SWITZICltL.\ND.

RED HALOGEN VAT-DYE AND PROCESS OF MAKING SAME.

Specification of Letters Patent.

Patented May 12, 1908.

Application filed October 1, 1907. Serial No. 395,424.

Example II. A mixture of H) parts of diof philosophy and chemist, a citizen of the Swiss ltepublic, and resident of Basel, Switzerland, have invented new and useful Red IIalogenated Vat-Dyes" and a Process of Making thefiame, of which the following is a full, clear, and exact specification.

In United States Patent No. 841003 dated January 8th 1907 is described a red vat-dye resulting from the condensation of salicylthioacetic acid with isatin and corresponding p obably to the formula i C,H C O C=C NH Since I have found, that exceedingly valn-i able halogen derivatives of this dye can be obtained by condensing 3-oiry-1-tliionaphthe'ne with halogen derivatives of an isatin co mpound. These dyes show relatively to the not halogenated dye the advantage of a greater al'finity to vegetable fibers and are.

' consequently distinguished by an excellent red coloration.

fastness to washing. The fastncss'to light is also inc eased.

The preparation of the said new dyes is illustrated by the following examples.

Example 5 parts of monobromisatin (prepared by brominating isatin in glacial acetic-acid), 3.5 parts of B-ox l-tliionapli thene and 50 parts of nitrobenzene are boiled together for two hours in a rellux ap iaratus; after cooling the separated dyestul' is isolated by iiltratitui, washed with alcohol and dried. It is obtained in the form of small yellow-rod crystals, soluble in concentrated sulfuric ac d to a dirty brown solution from which an addition of water precipitates the unchanged dyostuil' as scarlet-red flocks.

Funding sulfuric acid of St), dissolves.

the dyestuil' with a brown red coloration turning quicklyt'o blue-red; by pouring this solution 111 ice water a blue-red solution re sults. In hot benzene only traces of the dyestufl' dissolve with a clear rose coloration; lit-l dissolves hardly in cold nitrobenzene, but rather easily in hot nitrobenzenc with a deep i By itsT'treatment with the usual reducing agents the dyestuii yields a bright yellow at dyeing unmordan'ted cotton red tints.

bromisatin of melting point 248 C. (obtained by boiling in a reflux apparatus 5 parts of isatin with 25 parts of glacial acetic acid and 11 parts of bromin), 5 )arts of 3-oxyl-thionaphthenc and 80 partsol nitrobenzene, is heated in the oil bath in a rellux apparatus, for about 2 hours, the temperature of the oil bath being 226227 C. After cooling the mixture is filtered and the solid matter is washed with alcohol and dried. The condensation product is thus obtained in nearly quantitative yield as small lustrous, brownce'd crystals. Its solubility in benzene and nitrobenzene and the coloration of its sulfuric solutions are analogousto those of the monobromo derivative manufactured accordingly to the Example I. It dyes cotton in an alkaline va't clear red tints of very excellent fastness to washing, light and chlorin. The condensation may be effected in the presence of various solvents or condensing agents; in-

stead of in nitrobenzene; for instance in water or in alcohol. Inst'ad of using previously prepared 3 oxy-l-thionaphthene, salicylt'hioacetic acid may be used as the parent material together with an indifferent condensing agent which is capable of forming 3-oxy-l-thionaphthene from salicylthioa-' cetic acid under the conditions obtaining duripglthe reaction, for instance; acetic anhy- Example III. 10 partsof salicylthioacetic acid, 14.5 parts of dibromisatin and parts of acetic anhydrid are heated together to boiling,-in a reflux apparatus; after a short time the condensation product separates as small welldormed red crystals. After about 2 hours boiling the mixture is cooled, filtered and the solid matter washed with alcoho and dried; in this manner the product is obtained in very good yield and of satisfactory purity. with like result other halogen de rivatives of isatin and its homologucs may be substituted for the monobromisatin or the dibromisatin in the foregoing examples; as

for instance monochlorisatin, mon'obroin-ortho-methylisatin, dichlorisatin of melting point 205 208 C. (made by chlorinating isatin in glacial acetic acid) chlorobromisatin of melting point 233-234 (3., (obtainedby chlorinating bromisatin in glacial acetic acid) bromochlorisatin of melting point 243-246 C. (obtained by brominating chlorisatin in glacial acetic acid).

'hat I claim is:

1,. The process for the nmnufaolu 11a of hnlo- 5 gonuiml I'Oil val-(lycstull's by comlousing one molecule of tfi-oxjf-l-thionaphbhono with om: molecule of & halogenated isa'rin compound, as described.

2. The provess for the manufacture of hallogcnatod red vat (lyestufi's by boiling one tin oompounzl, uml *h are iamolul'lm 1n. (:ohl bonzno mull om'obonzohe, only sparmgly soluble 11; hot bow zone wlth a clear rose coloz-nliorl, ml her-r molly soluble in hot nitr0- Q benzene \vlth :1 deep red (:olor,d1ss0lvo in oo1 1- cent-rated sullm'lc and wuh a hrty brown IJ'lOlGCUlC ol' Salicylthiozwotiv acid with one 5 molecule ol :1 halogenated lszmn compound in presence of :1. comlel'lsing' agent capable of coloration, and yields on Lroatmont with al lmhno rmlucing' agents bright yellow vats, ll-om which Vals umnordanted cotton is dyed in JQll shzmos, fat-stv to Washing, light and ohlm'ln.

in witness whorool l: have hereunto signed my muno this 2001 (law): of September 1907, in the presence oi 1m) subscmbmg' \JIUF QBS.

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